Process for treating aged crude oil residue

ABSTRACT

The present invention provides a process for the treatment of crude oil or aged crude oil residue comprising the steps of (a) contacting the oil or residue with a phenol resin and with a diluent, to provide a diluted phenol resin treated oil or residue; and (b) optionally removing solid material from the diluted phenol resin treated oil or residue.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to the following InternationalApplications all by the current inventors Andrea Sneddon, et al:International Application No. PCT/GB2006/004834, entitled PROCESS; filedDec. 21, 2006; and GB 0526418.9 entitled PROCESS, filed on Dec. 23,2005, all of which are incorporated herein by reference in theirentirety.

The present invention relates to a process for the treatment of crudeoil or aged crude oil residue. The process mobilises crude oil or agedcrude oil residue allowing it to be used to provide saleable stableheavy fuel oil blend.

FIELD OF INVENTION

The present invention relates to the use of additives to allow crude oilor aged waste crude oil residue to be mixed with lighter hydrocarbonstreams to provide saleable stable heavy fuel oil blends. These may beused in furnace applications, boiler fuel, marine fuel, bunker fuel orblending components for bunker fuel, or bitumen.

The presence of the additive makes it possible to dilute the oil orwaste residue with lighter components that may otherwise have causedflocculation of asphaltenes and subsequent separation of the productinto two phases. Asphaltene flocculation causes problems such as sludgein tanks, slag in separators, plugging of filters, deposits on heatersand incomplete combustion.

The addition of additives resulted in an improved stability reserve, forexample as measured by a Turbiscan using ASTM D7061, of the aged wastecrude oil allowing it to be mixed with lighter fractions without phaseseparation occurring.

BACKGROUND

Finding a method to use refinery or other petroleum based wastes is aconsiderable problem. Currently available processes can be costly, timeconsuming and inefficient. A number of processes to do this have beendescribed in the prior art.

U.S. Pat. No. 4,990,237 discloses a method for oil recovery from wasteoil sludge by centrifugation, volatilisation, condensation andseparation by settling.

U.S. Pat. No. 4,897,205 covers the treatment of petroleum sludge by useof steam and a re-circulating solvent to decrease viscosity followed byseparation of the solid and liquid components by settlement. Furtherexamples are provided in WO 02/10293.

Asphaltenes are constituents of crude oils. They contain a multiplicityof structures, especially high molecular weight, fused aromaticcomponents and may contain heteroatoms such as O, N or and/or S. As theyare very complex, asphaltenes are generally defined in terms ofsolubility, e.g. soluble in benzene but not in n-pentane.

Asphaltenes can precipitate and be potentially problematical duringproduction, refining, transport and storage of crude oil and productsderived from crude oil, for example heavy fuel oil, residual fuel oil,Bunker C or marine fuel.

Depending on the final use of the oil problems can occur due toprecipitation of asphaltenes in valves and pipes and on hot surfacessuch as heat exchangers. In ships precipitation of asphaltenes can leadto poor combustion, handling and storage problems.

To reduce the viscosity of heavy and residual fuel oils dilution withsolvent is sometimes used. Here too handling and storage of the oils canbe disrupted by asphaltene precipitation.

Asphaltene dispersants for use in the above applications are alreadyknown. For example CA 2029465 and CA2075749 describealkylphenol-formaldehyde resins in combination withhydrophilic-lipophilic vinyl polymers.

The present invention alleviates the problems of the prior art.

In one aspect the present invention provides a process for the treatmentof crude oil or aged crude oil residue comprising the steps of (a)contacting the oil or residue with a phenol resin and with a diluent, toprovide a diluted phenol resin treated oil or residue; and (b)optionally removing solid material from the diluted phenol resin treatedoil or residue.

In one aspect the present invention provides a treated crude oil ortreated aged crude oil residue prepared by a process as defined herein.

In one aspect the present invention provides a residual fuel oil, boilerfuel, marine fuel, Bunker C, blending components for bunker fuel orbitumen comprising a treated crude oil or a treated aged crude oilresidue prepared by a process as defined herein.

In one aspect the present invention provides use of a phenol resin forincreasing the stability of a crude oil or an aged crude oil residue.

Further aspects of the invention are defined in the appended claims.

Surprisingly in an application to recover residual fuel oil from crudeoil or aged crude oil residue (residual pitch) it has been found thatthe use of additives during the process makes it possible to dilute thecrude oil or aged crude oil residue with lighter components that wouldotherwise have caused flocculation of asphaltenes. The inclusion ofadditives enables the production of saleable stable heavy fuel oilblends from these types of material.

It is understood that the phenol resin improves the stability reserve ofthe oil or residue compatibility and/or the compatibility betweenasphaltenes and the oil or residue. In particular it is believed thatthe addition of the phenol resin as require by the present invention mayincrease the compatibility of the “heavy fuel oil” components of theresidue with other components such as the diluent. Consequently onaddition of the diluent to the residue no problems are observed. Incontrast stability problems were observed when the residue withoutadditives was blended with diluent, such as a lighter feed stock.

Crude Oil

It will be understood that by the term “crude oil” it is meant unrefinedcrude oil. That is crude oil containing all fractions thereof.

In one aspect the crude oil is heavy crude oil. Heavy crude oil isunderstood to mean crude oil having an API gravity of less than 28degrees.

API gravity is the gravity or density of liquid petroleum productsdevised jointly by the American Petroleum Institute and the NationalBureau of Standards. The measuring scale is calibrated in terms ofdegrees API. The formula for determining API Gravity is as follows:Degrees API Gravity=(141.5/Specific Gravity at 60° F.)−131.5

Thus in a further aspect the present invention provides a process forthe treatment of heavy crude oil or aged crude oil residue comprisingthe steps of (a) contacting the heavy crude oil or residue with a phenolresin and with a diluent, to provide a diluted phenol resin treatedheavy crude oil or residue; and (b) optionally removing solid materialfrom the diluted phenol resin treated heavy crude oil or residue.

Aged Crude Oil Residue

The aged crude oil residues may be any residual component from crude oilrefining which have been aged by subsequent storage in the presence ofair.

A typical residual component is atmospheric residue, the residualcomponent from crude distillation, which has a boiling range startingfrom around 350° C.

Components from other processes such as visbreaking, thermal cracking orcatalytic cracking that are in this boiling range, or above, may also beconsidered.

In a preferred aspect the crude oil residues are from thermal crackingor atmospheric distillation that has been undertaken with processingconditions that have promoted cracking to increase gasoline anddistillate production but have produced a residual component of higherdensity, higher aromatics and asphaltene content, and containingincreased levels of coke.

The crude oil residue described herein, although normally useable infuel oil blending or as feedstocks for other processes, have beenrendered unusable by a combination of actual refinery processingoriginally undertaken and subsequent storage conditions. This may resultin a high density, high boiling point material with up to/over 30% ofassociated asphaltene, carbon particles and other solid (sand etc). Assuch the residue is not directly usable as a fuel oil or fuel oilcomponent because of the difficulties associated with handling, storageand distribution, combustion and blending.

In another aspect the crude oil residue may be materials that haveaccumulated as residues in tanks during distribution and storage ofcrude oil or heavy fuel oil products. An example is the sludge found inthe bottom of marine fuel tanks.

The crude oil residue may be aged for a period from production such thatit has been rendered unusable in fuel oil blending or as a feedstock

For example, the crude oil residue may be aged for a period of up to 1year from production, or for a period of up to 1 month from production,or for a period of at least 1 month from production, or for a period ofat least 1 year from production, or for a period of at least 2 yearsfrom production, or for a period of at least 3 years from production, orfor a period of at least 5 years from production, or for a period of atleast 10 years from production, or for a period of at least 20 yearsfrom production or for a period of at least 50 years from production.

Process

As discussed herein in a broad aspect the present invention provides aprocess for the treatment of crude oil or aged crude oil residuecomprising the steps of (a) contacting the oil or residue with a phenolresin and with a diluent, to provide a diluted phenol resin treated oilor residue; and (b) optionally removing solid material from the dilutedphenol resin treated oil or residue.

In one aspect an aged crude oil residue is treated. Thus there isprovided a process for the treatment of aged crude oil residuecomprising the steps of (a) contacting the residue with a phenol resinand with a diluent, to provide a diluted phenol resin treated residue;and (b) optionally removing solid material from the diluted phenol resintreated residue.

In one aspect crude oil is treated. Thus there is provided a process forthe treatment of crude oil comprising the steps of (a) contacting theoil with a phenol resin and with a diluent, to provide a diluted phenolresin treated oil; and (b) optionally removing solid material from thediluted phenol resin treated oil.

The phenol resin may be added to the oil or residue before addition ofthe diluent, after addition with the diluent, together with the diluentor combinations thereof. If the phenol resin and the diluent arecontacted with the oil or residue simultaneously, the phenol resin andthe diluent may be contacted separately, in combination or both.

In one preferred aspect the present invention provides a processcomprising the steps of

(a) contacting the oil or residue with the phenol resin to provide aphenol resin treated oil or residue

(b) combining the phenol resin treated oil or residue with the diluentto provide a diluted phenol resin treated oil or residue; and

(c) optionally removing solid material from the diluted phenol resintreated oil or residue.

In one preferred aspect the present invention provides a processcomprising the steps of

(a) combining the phenol resin and diluent

(b) contacting the combined phenol resin and diluent with the oil orresidue to provide a diluted phenol resin treated oil or residue, and

(c) optionally removing solid material from the diluted phenol resintreated oil or residue.

In one preferred aspect the present invention provides a processcomprising the steps of

(a) contacting the oil or residue with phenol resin to provide a treatedoil or residue

(b) separately to step (a), combining phenol resin and diluent toprovide a diluted phenol resin

(c) combining the treated oil or residue and the diluted phenol resin toprovide a diluted phenol resin treated oil or residue; and

(d) optionally removing solid material from the diluted phenol resintreated oil or residue.

In one preferred aspect then the oil or residue is contacted with thephenol resin (either alone or in combination with the diluent) it isheater and/or agitated.

As noted herein the removal of solid material from the diluted phenolresin treated oil or residue is optional. In a preferred aspect thisremoval is performed. Preferably the solid materials are removed byfiltration.

In one preferred aspect when the oil or residue is contacted with thephenol resin (either alone or in combination with the diluent) the oilor residue is at a temperature of 60-100° C.

In one preferred aspect when the diluent is contacted with the oil orresidue resin (either alone or in combination with the phenol resin) thediluent is at a temperature of 60-100° C.

In one preferred aspect the diluted oil or residue or the diluted phenolresin treated oil or residue is heated to a temperature of 80-110° C.for a period of 10 to 240 minutes.

In one preferred aspect the diluted oil or residue or the diluted phenolresin treated oil or residue is heated to a temperature of 80-110° C.for a period of 90 to 150 minutes.

In one preferred aspect the diluted phenol treated oil or residue iscooled prior to removal of solids.

Phenol Resin

In one aspect the phenol resin is a compound of Formula I

wherein m is at least 1; wherein n is at least 1; wherein the or each R₁is selected from alkyl groups, aromatic groups and heterocycles, andwherein ring A is optionally further substituted with groups selectedfrom —OH, hydrocarbyl groups, oxyhydrocarbyl groups, —CN, —NO₂, —SO₃H,—SO₂H, —COOH, —COOR₄, —NH₂, —NHR₅, —SO₂NH₂, —SO₂, —NHR₆, CONH₂, CONHR₇,SH and halogens; wherein each of R₄, R₅. R₆ and R₇ is independentlyselected from hydrocarbyl groups.

In one preferred aspect m is greater than 1. In one preferred aspect, mis 1 to 50, such as 1 to 40, 5 to 30, or 10 to 20. In a preferredaspect, m is 11 to 15.

n may be any suitable integer. For example n may be from 1 to 10 such as1 to 8, 1 to 5 or 1, 2 or 3. Preferably n is 1.

In one aspect the “linker” group may be branched. Thus in this aspectthe phenol resin may be a compound of Formula Ia

wherein m is at least 1; wherein n is at least 1; wherein the or each R₁is selected from alkyl groups, aromatic groups and heterocycles, andwherein ring A is optionally further substituted with groups selectedfrom —OH, hydrocarbyl groups, oxyhydrocarbyl groups, —CN, —NO₂, —SO₃H,—SO₂H, —COOH, —COOR₄, —NH₂, —NHR₅, —SO₂NH₂, —SO₂, —NHR₆, CONH₂, CONHR₇,SH and halogens; wherein each of R₄, R₅. R₆ and R₇ is independentlyselected from hydrocarbyl groups.

R₁ may be a linear or branched alkyl group.

In one aspect, preferably R₁ is a C₁-C₂₀₀ alkyl group, preferably aC₁-C₁₅₀ alkyl group, preferably a C₁₀-C₁₀₀ alkyl group, preferably aC₁-C₈₀ alkyl group, preferably a C₁-C₅₀ alkyl group, preferably a C₁-C₂₀alkyl group, preferably a C₅-C₂₀ alkyl group, preferably a C₅-C₁₅ alkylgroup, preferably a C₆-C₁₂ alkyl group, preferably a C₇-C₁₁ alkyl group,preferably a C₈-C₁₀ alkyl group, more preferably a C₉ alkyl group.

In one aspect, R₁ is a branched alkyl group, preferably a C₃₋₆ branchedalkyl group, for example t-butyl.

In one aspect, R₁ is a straight chain alkyl group.

In one aspect, preferably R₁ is a C₁-C₂₀₀ straight chain alkyl group,preferably a C₁-C₁₅₀ straight chain alkyl group, preferably a C₁₀-C₁₀₀straight chain alkyl group, preferably a C₁-C₈₀ straight chain alkylgroup, preferably a C₁-C₅₀ straight chain alkyl group, preferably aC₁-C₂₀ straight chain alkyl group, preferably a C₅-C₂₀ straight chainalkyl group, preferably a C₅-C₁₅ straight chain alkyl group, preferablya C₆-C₁₂ straight chain alkyl group, preferably a C₇-C₁₁ straight chainalkyl group, preferably a C₈-C₁₀ straight chain alkyl group, morepreferably a C₉ straight chain alkyl group.

In one preferred aspect R₁ is para substituted relative to the OH group.

In one preferred aspect the (CH₂)_(n) group is ortho substitutedrelative to the OH group.

Preferably R₁ is para substituted relative to the OH group and the(CH₂)_(n) group is ortho substituted relative to the OH group.

It will appreciated by one skilled in the art that the each of the“units” of Formula I may contain one or more further substituents. The“units” of Formula I independently of each other may be optionallysubstituted. As discussed herein ring A is optionally furthersubstituted with groups selected from —OH, hydrocarbyl groups,oxyhydrocarbyl groups, —CN, —NO₂, —SO₃H, —SO₂H, —COOH, —COOR₄, —NH₂,—NHR₅, —SO₂NH₂, —SO₂, —NHR₆, CONH₂, CONHR₇, SH and halogens; whereineach of R₄, R₅. R₆ and R₇ is independently selected from hydrocarbylgroups. In a preferred aspect at least one of the “units” isunsubstituted. In a further preferred aspect each of the “units” isunsubstituted.

Thus, in one aspect, the compound of Formula I is a compound of FormulaII

wherein the or each R₂ is an optional group independently selected from—OH, hydrocarbyl groups, oxyhydrocarbyl groups, —CN, —NO₂, —SO₃H, —SO₂H,—COOH, —COOR₄, —NH₂, —NHR₅, —SO₂NH₂, —SO₂, —NHR₆, CONH₂, CONHR₇, SH andhalogens; wherein each of R₄, R₅. R₆ and R₇ is independently selectedfrom hydrocarbyl groups; and wherein m, n and R₁ are as herein defined.

In a further aspect the compound is a compound of Formula IIa

wherein the or each R₂ is an optional group independently selected from—OH, hydrocarbyl groups, oxyhydrocarbyl groups, —CN, —NO₂, —SO₃H, —SO₂H,—COOH, —COOR₄, —NH₂, —NHR₅, —SO₂NH₂, —SO₂, —NHR₆, CONH₂, CONHR₇, SH andhalogens; wherein each of R₄, R₅. R₆ and R₇ is independently selectedfrom hydrocarbyl groups; and wherein m, n and R₁ are as herein defined.

Thus, in one aspect, the compound of Formula I is a compound of FormulaIII

wherein the or each R₂ and R₃ is an optional group independentlyselected from —OH, hydrocarbyl groups, oxyhydrocarbyl groups, —CN, —NO₂,—SO₃H, —SO₂H, —COOH, —COOR₄, —NH₂, —NHR₅, —SO₂NH₂, —SO₂, —NHR₆, CONH₂,CONHR₇, SH and halogens; wherein each of R₄, R₅. R₆ and R₇ isindependently selected from hydrocarbyl groups; and wherein m, n and R₁are as herein defined.

In a further aspect the compound is a compound of Formula IIIa

wherein the or each R₂ and R₃ is an optional group independentlyselected from —OH, hydrocarbyl groups, oxyhydrocarbyl groups, —CN, —NO₂,—SO₃H, —SO₂H, —COOH, —COOR₄, —NH₂, —NHR₅, —SO₂NH₂, —SO₂, —NHR₆, CONH₂,CONHR₇, SH and halogens; wherein each of R₄, R₅. R₆ and R₇ isindependently selected from hydrocarbyl groups; and wherein m, n and R₁are as herein defined.

In these aspects preferably R₂ and/or R₃ is an optional hydrocarbongroup, more preferably an optional linear or branched alkyl group.

The term “hydrocarbon” as used herein means any one of an alkyl group,an alkenyl group, an alkenyl group, an acyl group, which groups may belinear, branched or cyclic, or an aryl group. The term hydrocarbon alsoincludes those groups but wherein they have been optionally substituted.If the hydrocarbon is a branched structure having substituent(s)thereon, then the substitution may be on either the hydrocarbon backboneor on the branch; alternatively the substitutions may be on thehydrocarbon backbone and on the branch.

In this aspect, preferably R₂ and/or R₃ is an optional groupindependently selected from a C₁-C₅₀ group, preferably a C₁-C₄₀ group,preferably a C₁-C₃₀ group, preferably a C₁-C₂₅ group, preferably aC₁-C₁₅ group.

A typical example of R₂ or R₃ is a tertiary alkyl group, such as atertiary butyl group.

In a preferred aspect each of R₂ and R₃ are present such that ring A isfully substituted.

Preferably wherein ring A is optionally further substituted with groupsselected from —OH, hydrocarbyl groups, oxyhydrocarbyl groups, —CN, —NO₂,—SO₃H, —SO₂H, —COOH, —COOR₄, —NH₂, —NHR₅, —SO₂NH₂, —SO₂, —NHR₆, CONH₂,CONHR₇, SH and halogens; wherein each of R₄, R₅. R₆ and R₇ isindependently selected from hydrocarbyl groups.

In a preferred aspect the phenol resin is a substituted phenol resin.More preferably the phenol resin is the reaction product of substitutedphenol and an aldehyde.

More preferably the phenol resin is the reaction product of substitutedphenol and an aldehyde having 1-7 carbon atoms, for exampleformaldehyde.

In a preferred aspect the phenol resin is a nonyl phenol resin. Morepreferably the phenol resin is the reaction product of nonyl phenol andformaldehyde, or of t-butyl phenol and an aldehyde having 1-7 carbonatoms, for example formaldehyde.

Alkoxylated phenol resins (ethoxylated and/or propoxylated) areavailable. Their use is not excluded, but it is not preferred, asexcellent results have been obtained using non-alkoxylated phenolresins.

The phenol resin may be contacted with the oil or residue in anysuitable amount. Preferably the phenol resin is contacted with the oilor residue in an amount of 2 to 10,000 ppm based on the amount of oil orresidue, such as in an amount of 5 to 5,000 ppm based on the amount ofoil or residue, such as in an amount of 10 to 2,000 ppm based on theamount of oil or residue, or in an amount of 50 to 400 ppm based on theamount of oil or residue, or in an amount 200 to 350 ppm based on theamount of oil or residue.

Diluent

The diluent may be any suitable diluent

Typically the diluent is a crude oil distillation product selected fromkerosene, cracked gas oil, vacuum gas oil, long residue, short residue,heavy naptha, light gas oil, medium gas oil, heavy gas oil, cycle oil,gasoline, diesel and mixtures thereof.

Preferably the diluent is a vacuum gas oil. In one preferred aspect thediluent is a light vacuum gas oil. By the term “light vacuum gas oil” itis typically meant a gas oil fraction from a vacuum distillation tower,which will typically have a boiling range of 350-630° C.

Further Aspects

In a further aspect the present invention provides a treated crude oilor a treated aged crude oil residue prepared by a process as definedherein.

In a further aspect the present invention provides a treated crude oilor a treated aged crude oil residue obtainable by a process as definedherein.

In a further aspect a fuel (such as a residual fuel oil, boiler fuel ormarine fuel) comprising treated crude oil or treated aged crude oilresidue prepared by or obtainable a process as defined herein.

The fuel of the present invention (such as a residual fuel oil)typically has a density at 15° C. of no greater than 1010 kg/m³, forexample 960 kg/m³.

The fuel of the present invention (such as a residual fuel oil)typically has a pour point of no greater than 30° C., for example −14°C.

The fuel of the present invention (such as a residual fuel oil)typically has a flash point of at least 60° C., for example 129° C.

The fuel of the present invention (such as a residual fuel oil)typically has a sulphur content of no greater than 5 wt % for marinebunkers, or no greater than 3.5 wt % for land use.

The fuel of the present invention (such as a residual fuel oil)typically has a water content of no greater than 1% vol, for example nogreater than 0.1% vol.

The fuel of the present invention (such as a residual fuel oil)typically has a viscosity at 100° C. of 5 to 50 mm²/s, for example aviscosity at 50° C. of 42 mm²/s.

The present invention further provides use of a phenol resin forincreasing the stability of a crude oil or an aged crude oil residue.

The present invention further provides use of a phenol resin forincreasing the stability of asphaltenes in a crude oil or an aged crudeoil residue.

The present invention will now be described in further detail in thefollowing examples.

EXAMPLE 1 Testing Methology

A testing methology was devised which modelled the process used torecover aged crude oil residue and thus test the efficacy of additives.

The full scale process involves heating the residual pitch and moving toa blending vessel, blending in two stages with additive and diluents,filtration sludge removal and cooling.

The test methology used was as follows

-   1. Heat the pitch to 80° C., stir-   2. Add the additive to the pitch-   3. Heat the diluent (e.g. light vacuum gas oil) and add to the pitch    at 80° C.-   4. Stir the mixture and raise the temperature to 100° C.-   5. Maintain temperature for 30 minutes with stirring-   6. Raise the temperature to 120° C., maintain for 30 minutes with    stirring.-   7. Cool to 95° C. and filter through a 75 micron filter sieve.-   8. Test stability reserve of the oil by measuring separability    number, ASTM D7061-   9. Store the recovered heavy fuel oil blend at 45° C. for up to 30    days and test stability reserve using ASTM D7061.    Residue

The aged crude oil residue to be treated is residual pitch spread acrossa refinery with a pitch pond which has aged for 60+ years. The pitch isbasically the residue after thermal cracking which followed a simpledistillation and has the following properties:

Ash 0.7%

Asphaltenes 14.4%

Conradson Carbon Residue (CCR) 20.3%

Density 1.097

Fire point 230° C.

Heating Value 9335 kcal/kg,

Particle count NAS 1638

Pour point 30° C.

Sediment 3.63%

Sulphur 5.1%

Viscosity above 500000 cst @ 50° C.

Water 0.82%

Pb 13 ppm

Al 19 ppm

Si 41 ppm

Na 150 ppm,

Mo 17 ppm.

Additives

Additive 1—1:1 mix of resin A (below) and an oxyalkylated fatty amine.These 2 components are present at ˜16% individually in the mix.

Additive 2—phenol resin A (below) at 38 wt. % active ingredient ofPhenol resin A.

Additive 3—Similar to Additive 1 but further containing iron tallate.The materials are present in amounts of (i) 16 vol % resin A, (ii) 16vol % oxyalkylated fatty amine (to provide 16 vol % active material intotal since both are 50% concentration) and (iii) 50 vol % iron tallate.Additive 4—phenol resin B (below) at 38 wt. % active ingredient ofPhenol resin BAdditive 5—phenol resin B (below) at 55.8 wt. % active ingredient ofResin B.Resin A—50 wt. % active, nonyl phenol resin with CH₂ bridge+an ethyleneoxide/propylene oxide polymeric component.Mn 2468, Mw 3823, pd 1.55Resin B—˜70 wt. % active, nonyl phenol resin with CH₂ bridge.Mn 2680, Mw 3348, pd 1.74Results

Pitch residue was blended with light vacuum gas oil at a ratio of 1:1.The residue is diluted with Light Vacuum Gas Oil (LVGO) of 7 CSTreceived directly from refinery.

Total treat Separability Separability Separability Additive rate/ppmno. - Day 1 no. - Day 15 no. - Day 30 None 0 7.5 7.2 8.4 8.2 11.1 11.4Additive 1 400 0.08 0.08 3.22 3.38 5.5 5.3 Additive 2 400 0.11 0.14 0.200.28 1.12 1.14 Additive 3 400 0.16 0.12 4.1 4.1 6.7 6.8 Additive 4 4000.08 0.08 0.15 0.16 0.93 0.96 Additive 5 400 0.07 0.07 0.07 0.06 0.60.89

Separability number is a dimensionless parameter which measures thestability reserve of an oil.

When the separability number is between 0 and 5 the oil is considered tohave high stability reserve and asphaltenes are not likely toflocculate. If the separability number is between 5 and 10 the stabilityreserve is much lower, and asphaltenes may flocculate if the oil isexposed to conditions such as storage, ageing or heating. If theseparability number is greater than 10 the stability reserve is very lowand flocculation of asphaltenes may already have started.

FURTHER EXAMPLES

In example 1 we assessed separability. In subsequent examples we testedthe viscosity. Further, to evaluate the stability we provoked phaseseparation of the blended mixtures and studied the kinetics using alight scattering instrument.

In real use the fuel will be stored for 30 days at ˜50° C. and toevaluate the stability behaviour of the blends over time we stored themin an oven at ˜50° C. and checked whether and how much the phaseseparation changed over this time period.

In the further examples the pitch used was the same as in Example 1.Full characterising information about the additive(s) was not alwaysknown, but what is known is stated.

EXAMPLE 2 Checking Treat Rate

A testing methodology was devised to recover aged crude oil

Treat rates: 10, 100, 200, 500, 1000 and 2000 ppm phenol resin

Fuel: pitch+ light vacuum gas oil (LVGO)

We used a variety of treat rates in order to establish the minimum andmaximum level of additive required to make the crude oil residue (pitch)and vacuum gas oil blend stable and useable. To monitor the stability wemeasured the separability number. When adding the additive in excess, nogreat further improvement was to be seen.

The fuel was aged by storing it in an oven at 45° C. for 30 days and theseparability number was tested. This time period was chosen as it isrepresentative of the storage time the fuel is stored in tanks in ships.

The test methodology used was as follows.

-   -   1) Diluent and pitch were heated to 80° C. for 1 hour with        stirring    -   2) The phenol resin additive was added directly to the pitch    -   3) The pitch was then stirred every 5 minutes for 30 minutes at        80° C.    -   4) The diluent was then added to the pitch    -   5) The sample was stirred and heated at 90° C. for 30 minutes.        Stirring every 30 minutes.    -   6) The sample was then filtered through a 80 micron filter sieve    -   7) The oil blends stability reserve was tested by measuring the        separability number. ASTM D7067    -   8) The oil blends were then stored at 45° C. for 30 days. The        separability number was tested at days throughout.    -   9) Viscosity of the oil blends were also tested initially

The viscosity methodology was as follows.

Instrument T A Instruments AR2000 Rheometer

Measuring geometry—40 mm Parallel Plate

Gap—1000 micro meters

Peltier Plate—maintained at a temperature of 50° C.

-   -   1) Samples were kept at 50° C. to keep them in solution prior to        being transferred by pipette to the rheometer plate.    -   2) a preshear dependant on the initial viscosity of the samples        was applied to ensure that a homogeneous temperature gradient        was achieved across the sample and the sample shear history was        consistent.    -   3) a stress was then applied to the geometry that was consistent        with maintaining the sample between the parallel plates of the        geometry.    -   4) A run time of 300 minutes to ensure a stable viscosity.

All blended samples were aged in an oven for 30 days. The 30 day timeperiod is similar to the time that the fuel remains in the tank of aship. The samples were aged in an oven at 45 C and samples wereregularly taken out (after 1, 10, 21 and 30 days) and the separabilitynumber was measured.

The additives used were Resin B from Example 1.

Results

Total treat Rate/ Aging Separability Sample ppm (Days) Number Pitch andLVGO Blend No treatment 1 3.7 (50:50) Pitch and LVGO Blend No treatment10 6.2 (50:50) Pitch and LVGO Blend No treatment 21 4.5 (50:50) Pitchand LVGO Blend No treatment 30 6.8 (50:50) Pitch and LVGO Blend 10 ppmResin B 1 0.19 (50:50) Pitch and LVGO Blend 10 ppm Resin B 10 0.03(50:50) Pitch and LVGO Blend 10 ppm Resin B 21 0.45 (50:50) Pitch andLVGO Blend 10 ppm Resin B 30 2.2 (50:50) Pitch and LVGO Blend 100 PPMResin B 1 0.04 (50:50) Pitch and LVGO Blend 100 PPM Resin B 10 0.01(50:50) Pitch and LVGO Blend 100 PPM Resin B 21 0.04 (50:50) Pitch andLVGO Blend 100 PPM Resin B 30 0.27 (50:50) Pitch and LVGO Blend 200 ppmResin B 1 0.01 (50:50) Pitch and LVGO Blend 200 ppm Resin B 10 0.01(50:50) Pitch and LVGO Blend 200 ppm Resin B 21 0.06 (50:50) Pitch andLVGO Blend 200 ppm Resin B 30 0.05 (50:50) Pitch and LVGO Blend 500 ppmResin B 1 0.01 (50:50) Pitch and LVGO Blend 500 ppm Resin B 10 0.01(50:50) Pitch and LVGO Blend 500 ppm Resin B 21 0.01 (50:50) Pitch andLVGO Blend 500 ppm Resin B 30 0.02 (50:50) Pitch and LVGO Blend 1000 ppmResin B 1 0.01 (50:50) Pitch and LVGO Blend 1000 ppm Resin B 10 0.01(50:50) Pitch and LVGO Blend 1000 ppm Resin B 21 0.03 (50:50) Pitch andLVGO Blend 1000 ppm Resin B 30 0.02 (50:50) Pitch and LVGO Blend 2000ppm Resin B 1 0.01 (50:50) Pitch and LVGO Blend 2000 ppm Resin B 10 0.01(50:50) Pitch and LVGO Blend 2000 ppm Resin B 21 0.01 (50:50) Pitch andLVGO Blend 2000 ppm Resin B 30 0.02 (50:50)Viscosity Results

Conditions Pre Shear Additive Treat Applied Stress Sample rate ppmViscosity mPas Stress Pa Pitch N/A 473 50 1000 Pitch, LVGO 50:50 N/A 17510 20 Pitch, LVGO 50:50 Resin B 500 ppm 130 10 20

The base fuel alone is unusable due to its lack of mobility and beinghighly viscous. It can be seen that addition of diluent reducesviscosity; however the oil fuel/diluent blend is unstable as tested byseparability number. Addition of additive stabilises the fuel andreduces viscosity again.

EXAMPLE 3

A test methology was devised to understand if blending of additive tothe different components influenced the stability of the fuel. A treatrate of 500 ppm of Resin B of Example 1 was chosen as it is an effectivetreat rate to stabilise the fuel.

Resin B at the treat rate 500 ppm was added to fuel to diluent and toboth.

Test Methology

The same experimental procedure was followed as that used in experiment1 however additisation was made directly to the pitch or to the LVGO or250 ppm to pitch and 250 ppm to LVGO.

All temperatures remained the same as in example 2.

Results

Aging Separability Sample Additive (days) Number Pitch and LVGO 250 ppmResin B to 1 0.01 Blend (50:50) pitch + 250 ppm Resin B to LVGO Pitchand LVGO 250 ppm Resin B to 10 0.01 Blend (50:50) pitch + 250 ppm ResinB to LVGO Pitch and LVGO 250 ppm Resin B to 21 0.01 Blend (50:50)pitch + 250 ppm Resin B to LVGH Pitch and LVGO 250 ppm Resin B to 300.15 Blend (50:50) pitch + 250 ppm Resin B to LVGO Pitch and LVGO 500ppm Resin B to 1 0.01 Blend (50:50) pitch Pitch and LVGO 500 ppm Resin Bto 10 0.01 Blend (50:50) pitch Pitch and LVGO 500 ppm Resin B to 21 0.01Blend (50:50) pitch Pitch and LVGO 500 ppm Resin B to 30 0.02 Blend(50:50) pitch Pitch and LVGO 500 ppm Resin B to 1 0.01 Blend (50:50)LVGO Pitch and LVGO 500 ppm Resin B to 10 0.02 Blend (50:50) LVGO Pitchand LVGO 500 ppm Resin B to 21 0.01 Blend (50:50) LVGO Pitch and LVGO500 ppm Resin B to 30 0.05 Blend (50:50) LVGO

EXAMPLE 4

The idea behind this example was to investigate the effect of varyingthe diluents from LVGO to gasoline and diesel. These experiments werecarried out initially using the Pitch and latterly another fuel oil (seeexample 5).

Treat rate—500 ppm added to three heavy fuel oils diluted with threedifferent lighter fuels

Diluents—vacuum gas oil, light gas oil, and diesel in order to varyaromaticity.

Steps 1 to 4 were followed as in example 2. Steps 5-8 were:

-   -   5) Sample was stirred and heated at 40° C. for 30 minutes.        Stirring every 5 minutes.    -   6) Sample was then filtered through a 80 micron filter sieve    -   7) The oil blends stability reserve was tested by measuring the        separability number. ASTM D7067    -   8) The oil blends were then stored at 45° C. for 30 days. The        separability number was tested at days throughout.

The additive was Resin B of example 1.

Separability Sample Additive Aging (days) Number Diesel and pitch None 12.81 blend 50:50 Diesel and pitch None 10 3.87 blend 50:50 Diesel andpitch None 21 2.97 blend 50:50 Diesel and pitch None 30 5.7 blend 50:50Diesel and pitch 500 ppm Resin B 1 0.01 blend 50:50 Diesel and pitch 500ppm Resin B 10 0.02 blend 50:50 Diesel and pitch 500 ppm Resin B 21 0.11blend 50:50 Diesel and pitch 500 ppm Resin B 30 3.3 blend 50:50 Gasolineand pitch None 1 6.24 blend 50:50 Gasoline and pitch None 10 5.6 blend50:50 Gasoline and pitch None 21 6 blend 50:50 Gasoline and pitch None30 7.82 blend 50:50 Gasoline and pitch 500 ppm Resin B 1 0.14 blend50:50 Gasoline and pitch 500 ppm Resin B 10 0.04 blend 50:50 Gasolineand pitch 500 ppm Resin B 21 0.04 blend 50:50 Gasoline and pitch 500 ppmResin B 30 0.62 blend 50:50 LVGO and pitch None 1 3.68 blend 50:50 LVGOand pitch None 10 6.15 blend 50:50 LVGO and pitch None 21 4.39 blend50:50 LVGO and pitch None 30 6.7 blend 50:50 LVGO and pitch 500 ppmResin B 1 0.01 blend 50:50 LVGO and pitch 500 ppm Resin B 10 0.01 blend50:50 LVGO and pitch 500 ppm Resin B 21 0.01 blend 50:50 LVGO and pitch500 ppm Resin B 30 0.05 blend 50:50Viscosity Results

Analysis undertaken at 50° C.

Conditions Pre Shear Additive Treat Applied Stress Sample rate ppmViscosity mPas Stress Pa Pitch N/A 473 50 1000 Pitch, LVGO 50:50 N/A 17510 20 Pitch, LVGO 50:50 Resin B 500 ppm 130 10 20 Gasoline and pitch TWOPHASES Gasoline and Pitch Resin B 500 ppm 25 5 20

The additive provides a stable consistent oil blend in gasoline

EXAMPLE 5 Banias Crude Oil, Checking Importance of Diluent

Another heavy fuel oil sample (from Banias Refinery Company) was used.This fuel was chosen to show the effect of fuel that had not been storedfor as long as the pitch. It was also tested to provide evidence thatour additives have the ability to stabilise different fuels. Againdifferent diluents were used.

Test Methology

The same Experimental procedure was followed as in example 2.

The additive was Resin B of example 1.

Results

Separability Sample Additive Aging (days) Number Banias fuel and None 119.46 diesel Blend (50:50) Banias fuel and None 10 24.2 diesel Blend(50:50) Banias fuel and None 21 25.11 diesel Blend (50:50) Banias fueland None 30 25.2 diesel Blend (50:50) Banias fuel and None 1 12.7gasoline Blend (50:50) banias fuel and None 10 15.5 gasoline Blend(50:50) Banias fuel and None 21 26.2 gasoline Blend (50:50) Banias fueland None 30 25.6 gasoline Blend (50:50) Banias fuel and None 1 11.2 LGVOBlend (50:50) Banias fuel and None 10 19.7 LGVO Blend (50:50) Baniasfuel and None 21 17.3 LGVO Blend (50:50) Banias fuel and None 30 16 LGVOBlend (50:50) Banias fuel and 500 ppm of Resin B 1 6 diesel Blend(50:50) Banias fuel and 500 ppm of Resin B 10 6.6 diesel Blend (50:50)Banias fuel and 500 ppm of Resin B 21 2.4 diesel Blend (50:50) Baniasfuel and 500 ppm of Resin B 30 5.5 diesel Blend (50:50) Banias fuel and500 ppm of Resin B 1 3.65 gasoline Blend (50:50) Banias fuel and 500 ppmof Resin B 10 3.6 gasoline Blend (50:50) Banias fuel and 500 ppm ofResin B 21 1.9 gasoline Blend (50:50) Banias fuel and 500 ppm of Resin B30 3.55 gasoline Blend (50:50) Banias fuel and 500 ppm of Resin B 1 9.1LGVO Blend (50:50) Banias fuel and 500 ppm of Resin B 10 2.8 LGVO Blend(50:50) Banias fuel and 500 ppm of Resin B 21 3.8 LGVO Blend (50:50)Banias fuel and 500 ppm of Resin B 30 8.2 LGVO Blend (50:50)Viscosity Results

Analysis was undertaken at 50° C.

Conditions Pre Shear Additive Treat rate Applied Stress Sample ppmViscosity mPas Stress Pa Banias LVGO N/A 83 50 200 Banias LVGO FR59 500ppm 80 50 200 50:50

EXAMPLE 6 Evaluating the Performance of a Further Phenol Resin

Two phenol resins were tested in one heavy fuel oil (pitch) with onediluent (LVGO).

The same experimental procedure was followed as that used in example 2.

A further additive tested was Resin C-4 (1,1-dimethylethyl)phenolformaldehyde resin)

Results

Separability Sample Additive Aging (days) Number Pitch and LVGO 500 ppmof Resin C 1 0.03 Blend (50:50) to pitch Pitch and LVGO 500 ppm of ResinC 10 0.08 Blend (50:50) to pitch Pitch and LVGO 500 ppm of Resin C 210.02 Blend (50:50) to pitch Pitch and LVGO 500 ppm of Resin C 30 0.03Blend (50:50) to pitch

1. A process for the treatment of aged crude oil residue from crude oilrefining, which has been aged by subsequent storage in the presence ofair and which is unusable as a fuel oil or fuel oil component, theprocess comprising the steps of: (a) contacting the residue with aphenol resin and with a diluent, to provide a diluted phenol resintreated residue, wherein the diluent is a crude oil distillation productselected from the group consisting of: kerosene, cracked gas oil, vacuumgas oil, long residue, short residue, heavy naphtha, light gas oil,medium gas oil, heavy gas oil, cycle oil, gasoline, diesel and mixturesthereof.
 2. The process according to claim 1, wherein said contacting ofthe residue with the phenol resin occurs first to provide a phenol resintreated residue and is followed by combining the phenol resin treatedoil or residue with the diluent to provide a diluted phenol resintreated residue.
 3. The process according to claim 1, wherein prior tostep (a), is the step of combining the phenol resin and diluent.
 4. Theprocess according to claim 1 wherein aged crude oil residue is theresidue of atmospheric distillation or thermal cracking of crude oil. 5.The process according to claim 1 wherein the aged crude oil residue isaged for a period from production such that it has been renderedunusable in fuel oil blending or as a feedstock.
 6. The processaccording to claim 5 wherein the aged crude oil residue is aged for aperiod of at least 1 year from production.
 7. The process according toclaim 5 wherein the aged crude oil residue is aged for a period of atleast 2 year from production.
 8. The process according to claim 5wherein the aged crude oil residue is aged for a period of at least 10years from production.
 9. The process according to claim 1 wherein thephenol resin is the reaction product of a phenol and an aldehyde. 10.The process according to claim 9 wherein the aldehyde is formaldehyde.11. The process according to claim 1 wherein the phenol resin is acompound of Formula I

wherein m is at least 1; wherein n is at least 1; wherein the or each R₁is selected from alkyl groups, aromatic groups and heterocycles, andwherein ring A is optionally further substituted with groups selectedfrom —OH, hydrocarbyl groups, oxyhydrocarbyl groups, —CN, —NO₂, —SO₃H,—SO₂H, —COOH, —COOR₄, —NH₂, —NHR₅, —SO₂NH₂, —SO₂, —NHR₆, CONH₂, CONHR₇,SH and halogens; wherein each of R₄, R₅, R₆ and R₇ is independentlyselected from hydrocarbyl groups.
 12. The process according to claim 11wherein n is
 1. 13. The process according to claim 11 wherein R₁ is aC₆-C₁₂ alkyl group.
 14. The process according to claim 13 wherein R₁ isa C₉ alkyl group.
 15. The process according to claim 11 wherein R₁ is astraight chain alkyl group.
 16. The process according to claim 1 whereinthe phenol resin is a nonyl phenol resin.
 17. The process according toclaim 1 wherein the phenol resin is the reaction product of nonyl phenoland formaldehyde.
 18. The process according to claim 1 wherein thephenol resin is contacted with the residue in an amount of 10 to 10,000ppm based on the amount of residue.
 19. The process according to claim 1wherein the phenol resin is contacted with the residue in an amount of10 to 2,000 ppm based on the amount of residue.
 20. The processaccording to claim 1 wherein the phenol resin is contacted with theresidue in an amount of 50 to 400 ppm based on the amount of residue.21. The process according to claim 1 wherein the phenol resin iscontacted with the residue in an amount 200 to 350 ppm based on theamount of residue.
 22. The process according to claim 1 wherein thediluent is a vacuum gas oil.
 23. A diluted phenol resin treated residueprepared by the process according to claim
 1. 24. A residual oil, boilerfuel, marine fuel, Bunker C, blending components for bunker fuel orbitumen comprising the diluted phenol resin treated residue according toclaim
 23. 25. The process according to claim 1, wherein the stability ofthe aged crude oil residue is increased.
 26. The process according toclaim 25 wherein the stability of asphaltenes in the aged crude oilresidue is increased.
 27. The process according to claim 1 furthercomprising the step of removing solid material from the diluted phenolresin treated residue.
 28. The process according to claim 27 whereinsolid materials are removed by filtration.